CN114350955B - Treatment method for high value of each element in vanadium precipitation wastewater - Google Patents
Treatment method for high value of each element in vanadium precipitation wastewater Download PDFInfo
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- CN114350955B CN114350955B CN202111643279.1A CN202111643279A CN114350955B CN 114350955 B CN114350955 B CN 114350955B CN 202111643279 A CN202111643279 A CN 202111643279A CN 114350955 B CN114350955 B CN 114350955B
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 97
- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- 238000001556 precipitation Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 38
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims abstract description 130
- 239000007787 solid Substances 0.000 claims abstract description 84
- 239000000243 solution Substances 0.000 claims abstract description 66
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 42
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011575 calcium Substances 0.000 claims abstract description 40
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000002893 slag Substances 0.000 claims abstract description 26
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- 230000001105 regulatory effect Effects 0.000 claims abstract description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 16
- 239000011651 chromium Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims abstract description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 45
- 229920001223 polyethylene glycol Polymers 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 27
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 235000012771 pancakes Nutrition 0.000 claims description 15
- 229940037312 stearamide Drugs 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000378 calcium silicate Substances 0.000 claims description 10
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 10
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 9
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 9
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- -1 ammonium ions Chemical class 0.000 claims description 5
- 229940117975 chromium trioxide Drugs 0.000 claims description 5
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 3
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for treating high values of elements in vanadium precipitation wastewater, which comprises the following steps: regulating the pH value of vanadium precipitation wastewater, stirring and heating, and separating solid from liquid, wherein the solid is mixed calcium slag, and the liquid is a solution without ammonium, silicon and vanadium; adding a decalcifying agent into the solution, stirring, separating solid from liquid, wherein the solid is calcium carbonate, and the liquid is a solution without calcium; hexavalent chromium in the solution is converted into trivalent chromium; the trivalent chromium in the solution is converted into chromium hydroxide, solid-liquid separation is carried out, and chromium hydroxide is used for preparing chromium sesquioxide; evaporating and concentrating the solution, separating out sodium sulfate crystals in the solution, separating solid from liquid, and drying the solid to obtain high-purity anhydrous sodium sulfate; acid leaching solid mixed calcium slag, wherein vanadium in the solid enters the solution to form pure vanadium-containing solution, silicon and calcium in the solid form silicic acid and calcium sulfate to be separated out, and solid-liquid separation is carried out to extract vanadium from the pure vanadium-containing solution. The invention improves the recovery rate of chromium, prepares the high-purity anhydrous sodium sulfate by evaporating the high-purity sodium sulfate solution for removing vanadium and chromium impurities, and realizes the high-value utilization of elements in the vanadium precipitation wastewater.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for treating high values of elements in vanadium precipitation wastewater.
Background
The production process of the vanadium pentoxide mainly comprises two steps of sodium roasting of vanadium slag and calcification roasting of vanadium slag: crushing, ball milling and sieving vanadium slag, adding sodium carbonate or calcium compound mixture, roasting, leaching in water or acid to obtain vanadium-containing solution, controlling reasonable pH value, and adopting sulfuric acid and ammonium sulfate acid ammonium salt vanadium precipitation method to prepare vanadium pentoxide. The process generates a large amount of acid vanadium precipitation wastewater, and the main components of the acid vanadium precipitation wastewater are heavy metal ions such as vanadium, chromium, ammonium ions, chloride ions, sulfate radicals, sodium ions, a small amount of silicon ions, calcium ions and the like. At present, the treatment mode of the vanadium precipitation wastewater mainly comprises three stages of reduction, ammonium distillation and salt separation, but the problems of high treatment cost, low recovery rate of each element and the like still exist. Chinese patent CN107815549A adopts a reducing agent to reduce acidic wastewater, then uses calcium hydroxide or ammonia water to adjust the pH value to alkalescence, carries out solid-liquid separation, and recovers manganese and vanadium from the obtained filter residues through acid leaching. Although the method effectively recovers the manganese and vanadium in the wastewater, other high-value elements cannot be effectively recovered, and the method has low economic benefit and high treatment cost. Chinese patent CN1406882A adopts sulfur dioxide to reduce vanadium and chromium, then uses sodium hydroxide to adjust the alkali, solid-liquid separation is carried out, the solid is vanadium-chromium sediment, the liquid is discharged after ammonium evaporation, and the evaporated gas is absorbed by sulfuric acid to prepare ammonium sulfate. The method recovers vanadium and chromium together, but the separation of vanadium and chromium in the obtained vanadium-chromium precipitate is difficult, so that the vanadium-chromium recovery economic benefit is low, and other elements in the wastewater, such as sulfate radical, chloride ion and the like, cannot be effectively recovered. Chinese patent CN107089749A adopts ferric sulfate as vanadium precipitating agent to separate vanadium, sodium metabisulfite is used for reducing hexavalent chromium, sodium hydroxide is used for regulating alkalinity, solid-liquid separation is carried out, the solid is chromium hydroxide, and liquid is evaporated and concentrated after ammonium is removed by evaporation to prepare sodium sulfate. The method can effectively separate and recycle vanadium and chromium, but the pH value is regulated by sodium hydroxide in the process, so that the treatment cost is high. Therefore, the prior process for treating the vanadium precipitation wastewater is still to be continuously improved and explored.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for treating vanadium precipitation wastewater by high value of each element, comprising the steps of:
Step one, regulating the pH value of vanadium precipitation wastewater, stirring and heating, converting ammonium ions in the solution into ammonia gas to escape, converting vanadium and silicon in the solution into calcium vanadate and calcium silicate, carrying out solid-liquid separation, wherein the solid is mixed calcium slag of calcium vanadate, calcium silicate, calcium sulfate and calcium hydroxide, and the liquid is a solution without ammonium ions, silicon and vanadium;
step two, adding a decalcifying agent into the solution obtained in the step one, stirring, converting calcium in the solution into calcium carbonate, carrying out solid-liquid separation, wherein the solid is calcium carbonate, and the liquid is a solution without calcium;
Step three, adding a reducing agent into the solution obtained in the step two, regulating the pH value of the solution, stirring and reacting, and converting hexavalent chromium in the solution into trivalent chromium;
Regulating the pH value of the solution obtained in the step III, stirring, converting trivalent chromium in the solution into chromium hydroxide, carrying out solid-liquid separation, wherein the solid is the chromium hydroxide, and the liquid is a solution without hexavalent chromium, so as to prepare chromium sesquioxide by using the obtained chromium hydroxide;
Evaporating and concentrating the solution obtained in the step four, separating out sodium sulfate in the solution in a crystal form, carrying out solid-liquid separation, drying the solid to obtain high-purity anhydrous sodium sulfate, and returning the mother solution to circulation evaporation;
Step six, acid leaching is carried out on the solid mixed calcium slag obtained in the step one, vanadium in the solid enters the solution to form pure vanadium-containing solution, silicon and calcium in the solid form silicic acid and calcium sulfate to be separated out as solids, the solids are mixtures of the silicic acid and the calcium sulfate, the liquid is the pure vanadium-containing solution, and vanadium is extracted from the pure vanadium-containing solution.
Preferably, the method for adjusting the pH value of the vanadium precipitation wastewater in the first step comprises the following steps: adding alkaline substances into the vanadium precipitation wastewater; the alkaline substance is at least one of calcium oxide and calcium hydroxide, the pH value of the vanadium precipitation wastewater solution is adjusted to 10.5-13.5, the solution is stirred and heated to 90-100 ℃ after the pH value is adjusted, and then the solution is kept warm for 20-180 min.
Preferably, in the first step, the ammonia gas is absorbed by an ammonia gas absorbent, and the ammonia gas absorbent is at least one of sulfuric acid, hydrochloric acid and nitric acid.
Preferably, in the second step, the decalcifying agent is sodium carbonate, and the decalcifying agent is added according to the following amount of carbonate: the mole ratio of the simple substance calcium is 0.5-10:1, and the decalcification agent is added and stirred for 5-60 min.
Preferably, in the third step, the reducing agent is at least one of sodium sulfite, sodium metabisulfite and sulfur dioxide gas, and the adding amount of the reducing agent is as follows: the mol ratio of hexavalent chromium is 0.5-5:1; adding a reducing agent, then adjusting the pH value of the solution by using an acidic or alkaline substance, and stirring and reacting for 5-60 min, wherein the acidic substance is sulfuric acid, and the alkaline substance is sodium sulfide.
Preferably, in the fourth step, the method for adjusting the pH value of the solution is to add acidic or alkaline substances and then stir for 5-60 min; the alkaline substance for regulating pH value is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, in the sixth step, a sulfuric acid solution with the mass fraction of 20% -70% is added into the solid mixed calcium slag obtained in the first step, and the pH value of the mixed calcium slag slurry is adjusted to 2-4;
in the step six, the obtained pure vanadium-containing solution adopts an ammonium salt vanadium precipitation and hydrolysis vanadium precipitation process to prepare a vanadium product or returns to the front end of production to be mixed with the raw material liquid for extracting vanadium.
Preferably, the method for preparing the chromium trioxide by using the chromium hydroxide in the fourth step comprises the following steps:
S41, washing the chromium hydroxide solid by using hot water, and extruding the chromium hydroxide into a cake shape with the thickness of 15-32 mm after washing; transversely cutting cake-shaped chromium hydroxide into chromium hydroxide thin cakes with the diameter of 2-5 mm, processing a plurality of vent holes on each chromium hydroxide thin cake by using a needle, and putting the chromium hydroxide thin cakes into a drying device one by one for drying at the temperature of 110-180 ℃;
Step S42, primarily grinding the dried chromium hydroxide thin cake, adding quartz sand as a grinding aid, and screening the grinded chromium hydroxide to obtain chromium hydroxide coarse material;
S43, adding the chromium hydroxide coarse material obtained by grinding in the step S42 into a slurrying pool, adding water into the slurrying pool, stirring to form chromium hydroxide slurry, performing ultrasonic treatment after stirring, and controlling the ultrasonic frequency to be 36000-44000 Hz; after ultrasonic treatment for 1-2.5 h, adding a dispersing agent into the chromium hydroxide slurry, and then continuing stirring for 1.2-2 h at a stirring speed of 800-1200 rpm, wherein the dosage of the dispersing agent is 3.1-5.0% of the weight of the chromium hydroxide coarse material;
Step S44, filtering, evaporating, concentrating and washing the chromium hydroxide slurry prepared in the step S43, pressing the chromium hydroxide thin pancake to be 2-5 mm again, pricking a plurality of vent holes on the chromium hydroxide thin pancake, and then placing the chromium hydroxide thin pancake in a drying device for secondary drying;
And S45, crushing the secondarily dried chromium hydroxide thin cake, grinding, then placing the crushed chromium hydroxide thin cake into a rotary kiln or a calciner, calcining the crushed chromium hydroxide thin cake in a nitrogen atmosphere at the calcining temperature of 500-1100 ℃ to decompose chromium hydroxide into chromium oxide.
Preferably, the preparation method of the dispersant used in the step S43 is as follows:
Weighing 1.5-6 parts of polyethylene glycol and 0.5-1 part of stearamide according to parts by weight, dissolving the stearamide in 80-200 parts of ethanol, mixing, and carrying out ultrasonic oscillation for 1-2 hours;
Modifying polyethylene glycol by using maleic anhydride, adding polyethylene glycol and maleic anhydride into toluene, wherein the molar ratio of the polyethylene glycol to the maleic anhydride to the toluene is 7-10:1:25-38; argon is introduced into the reaction kettle, the introducing rate of the argon is 6sccm, the reaction temperature is 150 ℃, the reaction is carried out for 1.5 to 2 hours, then the reaction kettle is cooled to room temperature, the modified polyethylene glycol product in the reaction kettle is separated, carbon tetrachloride is used for completely dissolving the modified polyethylene glycol, then excessive diethyl ether is introduced into the solution, and pure modified polyethylene glycol crystal precipitate is generated in the solution;
and (3) crushing the modified polyethylene glycol crystals, adding the crushed modified polyethylene glycol crystals into ethanol in which stearamide is dissolved, stirring and mixing the crushed modified polyethylene glycol crystals, and completely evaporating the ethanol to prepare the dispersing agent.
The invention at least comprises the following beneficial effects: compared with the existing treatment scheme of vanadium precipitation wastewater, the invention has the advantages that: compared with the use of sodium hydroxide to adjust the pH value, the method has lower cost, and can convert vanadium into calcium vanadate, and then the calcium vanadate is leached by sulfuric acid to be converted into acid leaching solution capable of directly extracting vanadium, so that the complete separation of vanadium and chromium is realized.
The invention can directly deaminize the calcium-containing slurry through deamination treatment without deaminizing the calcium slag again, thereby further reducing the treatment cost of three wastes.
The invention carries out reduction treatment on the deamination liquid, can convert chromium in the wastewater into a high-purity chromium oxide green product, and improves the recovery rate of chromium element in the wastewater and the economic benefit thereof.
The high-purity sodium sulfate solution for removing impurities such as vanadium, chromium and the like can be evaporated to prepare high-purity anhydrous sodium sulfate, so that the high-value utilization of elements in the vanadium precipitation wastewater is realized.
When chromium hydroxide is used for calcining to prepare chromium sesquioxide, the invention carries out slurrying treatment on the chromium hydroxide, ultrasonic treatment on the chromium hydroxide slurry, and dispersion treatment on the chromium hydroxide slurry by using the modified polyethylene glycol and the dispersing agent with stearamide as main raw materials, so that the agglomeration of chromium hydroxide particles in the slurry is reduced, the efficiency of preparing the chromium sesquioxide by subsequent crushing and calcining of the chromium hydroxide is improved, and the particle size of the prepared chromium sesquioxide powder is smaller and more uniform.
In the invention, when the chromium hydroxide is dispersed, the modified polyethylene glycol and the stearamide are used as main raw materials, and when the modified polyethylene glycol is prepared, the polyethylene glycol is modified by the maleic anhydride, so that the dispersion performance of the polyethylene glycol is improved, and the chromium hydroxide slurry has excellent dispersion effect after being mixed with the stearamide.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is described in further detail below to enable those skilled in the art to practice the invention by reference to the specification.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Wherein, the components of the vanadium precipitation wastewater used in the examples are shown in the following table:
| Name of the name | V5+ | Cr6+ | Na+ | NH4 + | SO4 2- | Si |
| Content g/L | 0.1～1.0 | 0.5～5.0 | 30-60 | 0.5～10 | 60～100 | 0.1-1 |
Example 1:
a method for treating high-valued elements in vanadium precipitation wastewater comprises the following steps:
and adding 96.2g of calcium oxide into 8L of vanadium precipitation wastewater to adjust the pH value of the filtrate to 11, stirring for 150min, and then carrying out solid-liquid separation. The solid is calcium vanadate, calcium silicate, calcium sulfate and calcium hydroxide mixed calcium slag, the pH value of the calcium slag slurry can be regulated to 2.5 through a sulfuric acid solution with the mass fraction of 20%, silicon and calcium in the solid form silicic acid and calcium sulfate to be separated out as solids, the solids are a mixture of the silicic acid and the calcium sulfate, the liquid is a pure vanadium-containing solution, and the vanadium concentration is 31.8g/L; 27.8g of sodium carbonate was added to the filtrate, which was stirred for 10 minutes and then filtered. The solid is calcium carbonate, the pH value of the filtrate is regulated to 2-3 by sulfuric acid, 30.2g of sodium metabisulfite is added, the mixture is stirred and reacted for 10min, then sodium hydroxide is added to regulate the pH value to 7, and the solid and the liquid are separated. The solid is chromium hydroxide, chromium oxide green with the purity of 99.15 percent can be prepared after calcination at 1000 ℃, filtrate is filtered after once evaporation concentration, and 556.5g of anhydrous sodium sulfate with the purity of 98.89 percent is obtained after washing and drying the solid.
Example 2:
a method for treating high-valued elements in vanadium precipitation wastewater comprises the following steps:
73.1g of calcium oxide is added into 6L of vanadium precipitation wastewater to adjust the pH value of the filtrate to 11, and after stirring for 150min, solid-liquid separation is carried out. The solid is calcium vanadate, calcium silicate, calcium sulfate and calcium hydroxide mixed calcium slag, the pH value of the calcium slag slurry can be regulated to be 3 through a sulfuric acid solution with the mass fraction of 40%, silicon and calcium in the solid form silicic acid and calcium sulfate to be separated out as solids, the solids are a mixture of the silicic acid and the calcium sulfate, the liquid is a pure vanadium-containing solution, and the vanadium concentration is 33.4g/L; 21.3g of sodium carbonate was added to the filtrate, which was stirred for 10 minutes and then filtered. The solid is calcium carbonate, the pH value of the filtrate is regulated to 2-3 by sulfuric acid, 22.6g of sodium metabisulfite is added, the mixture is stirred and reacted for 10min, then sodium hydroxide is added to regulate the pH value to 7, and the solid and the liquid are separated. The solid is chromium hydroxide, chromium oxide green with the purity of 98.56% can be prepared by calcining at 1000 ℃, filtrate is filtered after once evaporation and concentration, and 562.8g of anhydrous sodium sulfate with the purity of 98.78% can be obtained after washing and drying the solid.
Example 3:
a method for treating high-valued elements in vanadium precipitation wastewater comprises the following steps:
84.9g of calcium oxide is added into 7L of vanadium precipitation wastewater to adjust the pH value of the filtrate to 11, and after stirring for 150min, solid-liquid separation is carried out. The solid is calcium vanadate, calcium silicate, calcium sulfate and calcium hydroxide mixed calcium slag, the pH value of the calcium slag slurry can be regulated to 3.5 by sulfuric acid with the mass fraction of 50%, silicon and calcium in the solid form silicic acid and calcium sulfate to be separated out as solid, the solid is a mixture of the silicic acid and the calcium sulfate, the liquid is pure vanadium-containing solution, and the vanadium concentration is 32.5g/L; 24.2g of sodium carbonate was added to the filtrate, which was stirred for 10 minutes and then filtered. The solid is calcium carbonate, the pH value of the filtrate is regulated to 2-3 by sulfuric acid, 27.2g of sodium metabisulfite is added, the mixture is stirred and reacted for 10min, then sodium hydroxide is added to regulate the pH value to 7, and the solid and the liquid are separated. The solid is chromium hydroxide, chromium oxide green with the purity of 99.03 percent can be prepared by calcining at 1000 ℃, filtrate is filtered after once evaporation concentration, and 551.4g of anhydrous sodium sulfate with the purity of 99.11 percent is obtained after washing and drying the solid.
Example 4:
a method for treating high-valued elements in vanadium precipitation wastewater comprises the following steps:
And adding 96.2g of calcium oxide into 8L of vanadium precipitation wastewater to adjust the pH value of the filtrate to 11, stirring for 150min, and then carrying out solid-liquid separation. The solid is calcium vanadate, calcium silicate, calcium sulfate and calcium hydroxide mixed calcium slag, the pH value of the calcium slag slurry can be regulated to 2.5 through a sulfuric acid solution with the mass fraction of 20%, silicon and calcium in the solid form silicic acid and calcium sulfate to be separated out as solids, the solids are a mixture of the silicic acid and the calcium sulfate, the liquid is a pure vanadium-containing solution, and the vanadium concentration is 31.8g/L; 27.8g of sodium carbonate was added to the filtrate, which was stirred for 10 minutes and then filtered. The solid is calcium carbonate, the pH value of the filtrate is regulated to 2-3 by sulfuric acid, 30.2g of sodium metabisulfite is added, the mixture is stirred and reacted for 10min, then sodium hydroxide is added to regulate the pH value to 7, and the solid and the liquid are separated. The solid is chromium hydroxide, the filtrate is filtered after once evaporation and concentration, and 556.5g of anhydrous sodium sulfate with the purity of 98.84% is obtained after washing and drying the solid.
The method for preparing the chromium trioxide by using the chromium hydroxide comprises the following steps of:
S41, washing chromium hydroxide solids by using hot water, and extruding the chromium hydroxide into a cake shape with the thickness of 15mm after washing; transversely cutting cake-shaped chromium hydroxide into chromium hydroxide thin cakes with the diameter of 2mm, processing a plurality of vent holes on each chromium hydroxide thin cake by using a needle, and putting the chromium hydroxide thin cakes into a drying device one by one for drying at the temperature of 110 ℃;
Step S42, primarily grinding the dried chromium hydroxide thin cake, adding quartz sand as a grinding aid, and screening the grinded chromium hydroxide to obtain chromium hydroxide coarse material;
step S43, adding the chromium hydroxide coarse material obtained by grinding in the step S42 into a slurrying pool, adding water into the slurrying pool, stirring to form chromium hydroxide slurry, carrying out ultrasonic treatment after stirring, and controlling the ultrasonic frequency to be 36000Hz; after ultrasonic treatment for 15 hours, adding a dispersing agent into the chromium hydroxide slurry, and then continuing stirring for 1.2 hours at a stirring speed of 900rpm, wherein the dosage of the dispersing agent is 3.1 percent of the weight of the chromium hydroxide coarse material;
Step S44, filtering, evaporating, concentrating and washing the chromium hydroxide slurry obtained in the step S43, pressing the chromium hydroxide thin cake into 2mm again, pricking a plurality of vent holes on the chromium hydroxide thin cake, and then placing the chromium hydroxide thin cake in a drying device for secondary drying;
and S45, crushing the secondarily dried chromium hydroxide thin pancake, grinding, and then placing the crushed chromium hydroxide thin pancake into a rotary kiln or a calciner, and calcining the crushed chromium hydroxide thin pancake in a nitrogen atmosphere at the calcining temperature of 1000 ℃ to prepare the chromium oxide with the purity of 99.17%.
The preparation method of the dispersing agent used in the step S43 comprises the following steps:
weighing 1.5 parts of polyethylene glycol and 0.5 part of stearamide according to parts by weight, dissolving the stearamide in 100 parts of ethanol, mixing, and carrying out ultrasonic oscillation for 1h;
Modifying polyethylene glycol by using maleic anhydride, adding polyethylene glycol and maleic anhydride into toluene, wherein the molar ratio of the polyethylene glycol to the maleic anhydride to the toluene is 7:1:25; argon is introduced into the reaction kettle, the introducing rate of the argon is 6sccm, the reaction temperature is 150 ℃, the reaction is carried out for 1.5 hours, then the reaction kettle is cooled to room temperature, the modified polyethylene glycol product in the reaction kettle is separated, carbon tetrachloride is used for completely dissolving the modified polyethylene glycol, then excessive diethyl ether is introduced into the solution, and pure modified polyethylene glycol crystal precipitate is generated in the solution;
and (3) crushing the modified polyethylene glycol crystals, adding the crushed modified polyethylene glycol crystals into ethanol in which stearamide is dissolved, stirring and mixing the crushed modified polyethylene glycol crystals, and completely evaporating the ethanol to prepare the dispersing agent.
10G of chromium oxide powder was taken and the particle size of the chromium oxide powder was measured, which indicated that the chromium oxide powder having a particle size of less than 18nm accounted for 96.33% of the total chromium oxide powder volume.
Example 5:
a method for treating high-valued elements in vanadium precipitation wastewater comprises the following steps:
and adding 96.2g of calcium oxide into 8L of vanadium precipitation wastewater to adjust the pH value of the filtrate to 11, stirring for 150min, and then carrying out solid-liquid separation. The solid is calcium vanadate, calcium silicate, calcium sulfate and calcium hydroxide mixed calcium slag, the pH value of the calcium slag slurry can be regulated to 2.5 through a sulfuric acid solution with the mass fraction of 20%, silicon and calcium in the solid form silicic acid and calcium sulfate to be separated out as solids, the solids are a mixture of the silicic acid and the calcium sulfate, the liquid is a pure vanadium-containing solution, and the vanadium concentration is 31.8g/L; 27.8g of sodium carbonate was added to the filtrate, which was stirred for 10 minutes and then filtered. The solid is calcium carbonate, the pH value of the filtrate is regulated to 2-3 by sulfuric acid, 30.2g of sodium metabisulfite is added, the mixture is stirred and reacted for 10min, then sodium hydroxide is added to regulate the pH value to 7, and the solid and the liquid are separated. The solid is chromium hydroxide, the filtrate is filtered after once evaporation and concentration, and 556.5g of anhydrous sodium sulfate with the purity of 98.81% is obtained after washing and drying the solid.
Preferably, the method for preparing the chromium trioxide by using the chromium hydroxide in the fourth step comprises the following steps:
s41, washing chromium hydroxide solids by using hot water, and extruding the chromium hydroxide into a cake shape with the thickness of 20mm after washing; transversely cutting cake-shaped chromium hydroxide into 5mm chromium hydroxide thin cakes, processing a plurality of vent holes on each chromium hydroxide thin cake by a needle, and drying the chromium hydroxide thin cakes one by one in a drying device at the drying temperature of 120 ℃;
Step S42, primarily grinding the dried chromium hydroxide thin cake, adding quartz sand as a grinding aid, and screening the grinded chromium hydroxide to obtain chromium hydroxide coarse material;
Step S43, adding the chromium hydroxide coarse material obtained by grinding in the step S42 into a slurrying pool, adding water into the slurrying pool, stirring to form chromium hydroxide slurry, carrying out ultrasonic treatment after stirring, and controlling the ultrasonic frequency to be 40000Hz; after ultrasonic treatment for 2 hours, adding a dispersing agent into the chromium hydroxide slurry, and then continuing stirring for 1.8 hours at a stirring speed of 1000rpm, wherein the dosage of the dispersing agent is 3.6% of the weight of the chromium hydroxide coarse material;
Step S44, filtering, evaporating, concentrating and washing the chromium hydroxide slurry obtained in the step S43, pressing the chromium hydroxide thin cake into a chromium hydroxide thin cake with the thickness of 5mm again, pricking a plurality of vent holes on the chromium hydroxide thin cake, and then placing the chromium hydroxide thin cake in a drying device for secondary drying;
And S45, crushing the secondarily dried chromium hydroxide thin pancake, grinding, and then placing the crushed chromium hydroxide thin pancake into a rotary kiln or a calciner, and calcining the crushed chromium hydroxide thin pancake in a nitrogen atmosphere at the calcining temperature of 1000 ℃ to prepare the chromium oxide with the purity of 99.08%.
The preparation method of the dispersing agent used in the step S43 comprises the following steps:
Weighing 2 parts of polyethylene glycol and 1 part of stearamide according to parts by weight, dissolving the stearamide in 140 parts of ethanol, mixing, and carrying out ultrasonic oscillation for 1.6 hours;
modifying polyethylene glycol by using maleic anhydride, adding polyethylene glycol and maleic anhydride into toluene, wherein the molar ratio of the polyethylene glycol to the maleic anhydride to the toluene is 10:1:29; argon is introduced into the reaction kettle, the introducing rate of the argon is 6sccm, the reaction temperature is 150 ℃, the reaction is carried out for 1.5 hours, then the reaction kettle is cooled to room temperature, the modified polyethylene glycol product in the reaction kettle is separated, carbon tetrachloride is used for completely dissolving the modified polyethylene glycol, then excessive diethyl ether is introduced into the solution, and pure modified polyethylene glycol crystal precipitate is generated in the solution;
and (3) crushing the modified polyethylene glycol crystals, adding the crushed modified polyethylene glycol crystals into ethanol in which stearamide is dissolved, stirring and mixing the crushed modified polyethylene glycol crystals, and completely evaporating the ethanol to prepare the dispersing agent.
10G of chromium oxide powder was taken and the particle size of the chromium oxide powder was measured, which indicated that the chromium oxide powder having a particle size of less than 18nm accounted for 95.72% of the total chromium oxide powder volume.
Comparative example
A method for treating high-valued elements in vanadium precipitation wastewater comprises the following steps:
And adding 96.2g of calcium oxide into 8L of vanadium precipitation wastewater to adjust the pH value of the filtrate to 11, stirring for 150min, and then carrying out solid-liquid separation. The solid is calcium vanadate, calcium silicate, calcium sulfate and calcium hydroxide mixed calcium slag, the pH value of the calcium slag slurry can be regulated to 2.5 through a sulfuric acid solution with the mass fraction of 20%, silicon and calcium in the solid form silicic acid and calcium sulfate to be separated out as solids, the solids are a mixture of the silicic acid and the calcium sulfate, the liquid is a pure vanadium-containing solution, and the vanadium concentration is 31.8g/L; 27.8g of sodium carbonate was added to the filtrate, which was stirred for 10 minutes and then filtered. The solid is calcium carbonate, the pH value of the filtrate is regulated to 2-3 by sulfuric acid, 30.2g of sodium metabisulfite is added, the mixture is stirred and reacted for 10min, then sodium hydroxide is added to regulate the pH value to 7, and the solid and the liquid are separated. The solid is chromium hydroxide, the filtrate is filtered after once evaporation and concentration, and 556.5g of anhydrous sodium sulfate with the purity of 98.83% is obtained after washing and drying the solid.
Preferably, the method for preparing the chromium trioxide by using the chromium hydroxide in the fourth step comprises the following steps:
s41, washing chromium hydroxide solids by using hot water, and extruding the chromium hydroxide into a cake shape with the thickness of 20mm after washing; transversely cutting cake-shaped chromium hydroxide into 5mm chromium hydroxide thin cakes, processing a plurality of vent holes on each chromium hydroxide thin cake by a needle, and drying the chromium hydroxide thin cakes one by one in a drying device at the drying temperature of 120 ℃;
Step S42, primarily grinding the dried chromium hydroxide thin cake, adding quartz sand as a grinding aid, and screening the grinded chromium hydroxide to obtain chromium hydroxide coarse material;
Step S43, adding the chromium hydroxide coarse material obtained by grinding in the step S42 into a slurrying pool, adding water into the slurrying pool, and stirring to obtain chromium hydroxide slurry;
Step S44, filtering, evaporating, concentrating and washing the chromium hydroxide slurry obtained in the step S43, pressing the chromium hydroxide thin cake into a chromium hydroxide thin cake with the thickness of 5mm again, pricking a plurality of vent holes on the chromium hydroxide thin cake, and then placing the chromium hydroxide thin cake in a drying device for secondary drying;
And S45, crushing the secondarily dried chromium hydroxide thin pancake, grinding, and then placing the crushed chromium hydroxide thin pancake into a rotary kiln or a calciner, and calcining the crushed chromium hydroxide thin pancake in a nitrogen atmosphere at the calcining temperature of 1000 ℃ to prepare the chromium oxide with the purity of 99.11%.
10G of chromium oxide powder was taken and the particle size of the chromium oxide powder was measured, and the result showed that the chromium oxide powder having a particle size of less than 18nm accounted for 73.15% of the total volume of the chromium oxide powder.
The number of equipment and the scale of processing described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be readily apparent to those skilled in the art.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (7)
1. The high-valued treatment method for each element in the vanadium precipitation wastewater is characterized by comprising the following steps of:
step one, regulating the pH value of vanadium precipitation wastewater, stirring and heating, and carrying out solid-liquid separation, wherein the solid is calcium vanadate, calcium silicate, mixed calcium slag of calcium sulfate and calcium hydroxide, and the liquid is a solution without ammonium, silicon and vanadium;
step two, adding a decalcifying agent into the solution obtained in the step one, stirring, converting calcium in the solution into calcium carbonate, carrying out solid-liquid separation, wherein the solid is calcium carbonate, and the liquid is a solution without calcium;
Step three, the pH value of the filtrate is regulated to 2-3 by an acidic substance or an alkaline substance, a reducing agent is added, and the solution is stirred and reacted to convert hexavalent chromium into trivalent chromium;
Regulating the pH value of the solution obtained in the step III, stirring, converting trivalent chromium in the solution into chromium hydroxide, carrying out solid-liquid separation, and preparing chromium sesquioxide from the obtained chromium hydroxide;
evaporating and concentrating the solution obtained in the step four, separating out sodium sulfate crystals from the solution, separating solid from liquid, drying the solid to obtain high-purity anhydrous sodium sulfate, and returning the mother solution to circulation evaporation;
Step six, adding a sulfuric acid solution with the mass fraction of 20% -70% into the solid mixed calcium slag obtained in the step one, carrying out acid leaching on the solid mixed calcium slag obtained in the step one, enabling vanadium in the solid to enter the solution to form a pure vanadium-containing solution, enabling silicon and calcium in the solid to form silicic acid and calcium sulfate to be separated out in a solid mode, carrying out solid-liquid separation, and extracting vanadium from the pure vanadium-containing solution, wherein the solid is a mixture of the silicic acid and the calcium sulfate;
the method for preparing the chromium trioxide by using the chromium hydroxide in the fourth step comprises the following steps of:
S41, washing chromium hydroxide solids by using hot water, and extruding the chromium hydroxide into cakes after washing, wherein the thickness of the chromium hydroxide is 15-32 mm; transversely cutting cake-shaped chromium hydroxide into 2-5 mm chromium hydroxide thin cakes, processing a plurality of vent holes on each chromium hydroxide thin cake by using a needle, and drying the chromium hydroxide thin cakes in a drying device one by one at 110-180 ℃;
Step S42, primarily grinding the dried chromium hydroxide thin cake, adding quartz sand as a grinding aid, and screening the grinded chromium hydroxide to obtain chromium hydroxide coarse material;
Step S43, adding the chromium hydroxide coarse material obtained by grinding in the step S42 into a slurrying pool, adding water into the slurrying pool, stirring to form chromium hydroxide slurry, carrying out ultrasonic treatment after stirring, and controlling the ultrasonic frequency to be 36000-4400Hz; after ultrasonic treatment for 1-2.5 h, adding a dispersing agent into the chromium hydroxide slurry, and then continuously stirring for 1.2-2 h at a stirring speed of 800-1200 rpm, wherein the consumption of the dispersing agent accounts for 3.1% -5.0% of the weight of the chromium hydroxide coarse material;
step S44, filtering, evaporating, concentrating and washing the chromium hydroxide slurry prepared in the step S43, pressing the chromium hydroxide thin pancake with the thickness of 2-5 mm again, pricking a plurality of vent holes on the chromium hydroxide thin pancake, and then placing the chromium hydroxide thin pancake in a drying device for secondary drying;
step S45, crushing the secondarily dried chromium hydroxide thin cake, grinding, then placing the crushed chromium hydroxide thin cake into a rotary kiln or a calciner, calcining the crushed chromium hydroxide thin cake in a nitrogen atmosphere at the calcining temperature of 500-1100 ℃ to decompose chromium hydroxide into chromium oxide;
the preparation method of the dispersing agent used in the step S43 comprises the following steps:
Weighing 1.5-6 parts of polyethylene glycol and 0.5-1 part of stearamide according to parts by weight, dissolving the stearamide in 80-200 parts of ethanol, mixing, and carrying out ultrasonic oscillation for 1-2 hours;
Modifying polyethylene glycol by using maleic anhydride, and adding the polyethylene glycol and the maleic anhydride into toluene, wherein the molar ratio of the polyethylene glycol to the maleic anhydride to the toluene is 7-10:1:25-38; argon is introduced into the reaction kettle, the introducing rate of the argon is 6sccm, the reaction temperature is 150 ℃, the reaction is carried out for 1.5-2 hours, then the reaction kettle is cooled to room temperature, the modified polyethylene glycol product in the reaction kettle is separated, carbon tetrachloride is used for completely dissolving the modified polyethylene glycol, then excessive diethyl ether is introduced into the solution, and pure modified polyethylene glycol crystal precipitate is generated in the solution;
crushing the modified polyethylene glycol crystals, adding the crushed modified polyethylene glycol crystals into ethanol dissolved with stearamide, stirring and mixing the crushed modified polyethylene glycol crystals, and completely evaporating the ethanol to prepare the dispersing agent;
The method for adjusting the pH value of the vanadium precipitation wastewater in the first step comprises the following steps: adding alkaline substances into the vanadium precipitation wastewater, and adjusting the pH value of the vanadium precipitation wastewater solution to 10.5-13.5;
In the second step, the decalcifying agent is sodium carbonate.
2. The method for treating vanadium wastewater with high element values according to claim 1, wherein in the first step, the alkaline substance is at least one of calcium oxide and calcium hydroxide, and the alkaline substance is heated to 90-100 ℃ with stirring after adjusting the pH value, and then is kept for 20-180 min.
3. The method for treating vanadium wastewater with high element values according to claim 1, wherein in the first step, after stirring and heating to 90-100 ℃, ammonium ions in the solution are converted into ammonia gas to escape, and vanadium and silicon in the solution are converted into calcium vanadate and calcium silicate; and absorbing the escaped ammonia by using an ammonia absorbent, wherein the ammonia absorbent is at least one of sulfuric acid, hydrochloric acid and nitric acid.
4. The method for treating vanadium wastewater with high values of elements according to claim 1, wherein in the second step, the decalcifying agent is added according to the following amount of carbonate: the molar ratio of the simple substance calcium is 0.5-10:1, and the mixture is stirred for 5-60 min after the decalcification agent is added.
5. The method for treating vanadium wastewater with high values according to claim 1, wherein in the third step, the reducing agent is at least one of sodium sulfite, sodium metabisulfite and sulfur dioxide gas, and the adding amount of the reducing agent is as follows: the mol ratio of hexavalent chromium is 0.5-5:1; stirring and reacting for 5-60 min, wherein the acidic substance is sulfuric acid and the alkaline substance is sodium sulfide.
6. The method for treating vanadium wastewater with high element values according to claim 1, wherein in the fourth step, the method for adjusting the pH value of the solution is to add acidic or alkaline substances and then stir for 5-60 min; the alkaline substance for regulating pH value is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
7. The method for treating vanadium wastewater with high element values according to claim 1, wherein in the step six, the acid leaching is performed by adjusting the pH value of the mixed calcium slag slurry to 2-4;
in the step six, the obtained pure vanadium-containing solution adopts an ammonium salt vanadium precipitation and hydrolysis vanadium precipitation process to prepare a vanadium product or returns to the front end of production to be mixed with the raw material liquid for extracting vanadium.
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| DE10217207A1 (en) * | 2002-04-18 | 2003-11-06 | Bayer Ag | Process for recycling vanadium in chrome ore as ammonium metavanadate |
| CN101358282A (en) * | 2008-08-26 | 2009-02-04 | 攀钢集团研究院有限公司 | A method for circularly desorbing vanadium-containing resin with vanadium precipitation wastewater |
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| CN106893877A (en) * | 2017-02-27 | 2017-06-27 | 中南大学 | A kind of method that vanadium chromium is extracted in the chromic acid mixed salt solution from vanadium |
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| DE10217207A1 (en) * | 2002-04-18 | 2003-11-06 | Bayer Ag | Process for recycling vanadium in chrome ore as ammonium metavanadate |
| CN101358282A (en) * | 2008-08-26 | 2009-02-04 | 攀钢集团研究院有限公司 | A method for circularly desorbing vanadium-containing resin with vanadium precipitation wastewater |
| CN104086032A (en) * | 2014-07-30 | 2014-10-08 | 攀钢集团攀枝花钢钒有限公司 | Method for recycling vanadium precipitating wastewater |
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